Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
  • C10M135/10—Sulfonic acids or derivatives thereof

Definitions

• Sulfonates particularly calcium, barium or magnesium overbased sulfonates are widely used as additives for lubricating oils.
• the term “overbased” is used to describe sulfonates containing an amount of metal in excess of that required to react with the sulfonic acid from which the sulfonate is obtained. Frequently, the excess metal is in the form of its carbonate, in which case the overbased sulfonate consists of a colloidal dispersion of the metal carbonate in the metal sulfonate as dispersant.
• These overbased sulfonates are used as dispersants in the lubricating oil where their basicity neutralizes acids which develop in the crank cases of engines during engine operation, thus reducing corrosion.
• Sulfonates are generally obtained from monoalkylates of aromatics, the alkyl chain being either branched or straight.
• Oil soluble sulfonates are obtained from alkylates containing an alkyl group of more than 16, generally more than 20, carbon atoms.
• WO 96/26919 discloses low base number sulfonates which are said to be useful in lubricants.
• the sulfonates are prepared from high molecular weight sulfonic acids (i.e., they have a number average molecular weight of 500 or higher).
• the high molecular weight sulfonic acids may be alkaryl sulfonic acids, for example alkyl benzene sulfonic acid, alkyl toluene sulfonic acid or alkylxylene sulfonic acid.
• the sulfonic acid is a mixed sulfonic acid of C 15 to C 60 and higher alkyl benzene or C 15 to C 60 and higher alkyl xylene or C 15 to C 60 and higher alkyl toluene sulfonic acids.
• a lower molecular weight sulfonic acid may also be used. It is preferably an alkylaryl sulfonic acid and most preferably a mixture of C 8 to C 30 and higher alkyl substituted alkyl benzene or alkyl toluene or alkyl xylene sulfonic acid. It is preferred that the lower molecular weight sulfonic acid has a number average molecular weight of at least 300, preferably at least 350.
• the preferred high molecular weight sulfonic acids and when present lower molecular weight sulfonic acids are said to be those which are derived from aromatic alkylates prepared from C 2 , C 3 or C 4 polyolefins such as polyethylene, polypropylene or polynormal butene. It is also said to be possible to prepare straight chain lower molecular weight sulfonic acids from aromatic alkylates prepared from straight chain hydrocarbons such as linear alpha-olefins.
• U.S. Pat. No. 4,235,810 issued Nov. 25, 1980 to Osselet et al., discloses alkyl aromatics prepared by alkylation with a mixture of straight and branched chain olefins containing 16 to 30 carbon atoms. Oligomers of propylene are said to be the preferred branched chain olefin.
• the alkyl aromatics can be converted to sulfonates having a Total Base Number of 300.
• U.S. Pat. No. 4,259,193, issued Mar. 31, 1981 to Tirtiaux et al. discloses overbased alkaline earth metal mono-alkyl ortho-xylene in which the alkylaryl moiety is a mono-alkyl ortho-xylene or a mono-alkyl toluene and the alkyl group contains 15 to 40 carbon atoms.
• the alkyl group may be straight chain or branched. Oligomers of propylene may be used for the alkyl group.
• the overbased sulfonates have a Total Base Number of 300.
• the alkyl sulfonic acid used to prepared the sulfonate should preferably have at least 18 carbon atoms in the alkyl chain.
• Alkaryl sulfonic acids having a molecular weight of between 300 and 700, e.g., between 400 and 500, such as alkyl benzene and alkyl toluene sulfonic acids are said to be suitable.
• the alkyl group may be straight chain or branched.
• a low overbased alkaline earth metal alkylaryl sulfonate having a Total Base Number of from about 2 to about 30, a dialkylate content of 0% to about 25% and a monoalkylate content of about 75% to about 90% or more, wherein the alkylaryl moiety is alkyltoluene or alkylbenzene in which the alkyl group is a C 15 -C 21 branched chain alkyl group derived from a propylene oligomer.
• the present invention also provides a lubricating oil containing a low overbased alkaline earth metal alkylaryl sulfonate having a Total Base Number of from about 2 to about 30, a dialkylate content of 0% to about 25% and a monoalkylate content of about 75% to about 90% or more, wherein the alkylaryl moiety is alkyltoluene or alkylbenzene in which the alkyl group is a C 15 -C 21 branched chain alkyl group derived from a propylene oligomer.
• a lubricating oil formulation comprising:
• the present invention further provides a concentrate comprising about from 10 weight % to 90 weight % of a compatible organic liquid diluent and about from 0.5 weight % to 90 weight % of a low overbased alkaline earth metal alkylaryl sulfonate having a Total Base Number of from about 2 to about 30, a dialkylate content of 0% to about 25% and a monoalkylate content of about 75% to about 100%, wherein the alkylaryl moiety is alkyltoluene or alkylbenzene in which the alkyl group is a C 15 -C 21 branched chain alkyl group derived from a propylene oligomer.
• a method of producing a lubricating oil composition comprising blending the following components together:
• the present invention also provides the lubricating oil composition produced by this method.
• the present invention also provides an improved method of preparing an alkaline earth metal alkyltoluene sulfonate by reacting an alkyltoluene sulfonic acid with an active source of alkaline earth metal in the presence of a solvent, wherein the improvement comprises using water as the solvent.
• the low overbased alkylaryl sulfonates of the present invention are prepared from alkylates of benzene and toluene.
• the alkylates may be prepared by Friedel-Crafts alkylation of the benzene or toluene using techniques known in the art.
• the alkylates used to prepare the sulfonates of this invention are prepared using a propylene oligomer for the alkyl group.
• the propylene oligomers useful for this purpose have an average of about 15 to 21, preferably about 14 to 18, carbon atoms.
• the oligomers have a low di-olefin content, i.e., they have a Bromine Number of about 15 to about 25 mg/100 g.
• the synthesis of the alkyltoluene alkylate can be accomplished by the alkylation of toluene with the propylene oligomer described below using a variety of Lewis or Bronsted acid catalysts.
• Typical commercial catalysts include, but are not limited to, phosphoric acid/kieselguhr, aluminum halides, boron trifluoride, antimony chloride, stannis chloride, zinc chloride, onium poly(hydrogen fluoride), and hydrogen fluoride.
• Other catalysts include solid acidic catalysts that have at least one metal oxide, such as natural zeolites, synthetic zeolites, synthetic molecular sieves, and clays.
• the alkylation of toluene can produce a variety of products. These include, but are not limited to, isomeric mono-alkylated toluenes, such as ortho-alkyltoluene, meta-alkyltoluene, and para-alkyltoluene. Other products can include di-alkylated and/or polyalkylated toluene products and their isomers.
• the preferred toluene alkylate is one which affords acceptable sulfonation yields.
• GLPC analysis of the preferred alkylated toluene product reveals that it is composed of three major fractions which are referred to herein as Light Product, Heartcut Product, and Heavies Product.
• GLPC analysis of the toluene alkylate is accomplished using a Varian 6100 gas chromatograph equipped with an FID detector operating with the following column and instrument conditions:
• the resulting chromatogram is analyzed in the following manner to determine the percentage of Light, Heartcut, and Heavies distribution:
• Percent Light Product content Absolute of peaks eluting between 15.05 and 30 minutes/Area of peaks eluting between 15.05 and 80 minutes
• Percent Heartcut Product content Average of peaks eluting between 30.05 and 45 minutes/Area of peaks eluting between 15.05 and 80 minutes
• Percent Heavies Product content Average of peaks eluting between 45.05 and 80 minutes/Area of peaks eluting between 15.05 and 80 minutes
• the preferred toluene alkylates of this invention contain about 0-15% Light Product, about 75-90% Heartcut Product, and about 0-15% Heavies Product.
• the toluene alkylate can also be analyzed by IR by recording the absorbance IR spectrum of the product as a film on salt block cells.
• the IR spectrum is scaled to the 650-1000 cm ⁇ 1 region and plotted.
• the isomer distribution is calculated as follows:
• Percent ortho isomer content Height of peak at 705 cm ⁇ 1 /Sum of the peak heights at 705 cm ⁇ 1 , 785 cm ⁇ 1 , and 815 cm ⁇ 1
• Percent meta isomer content Height of peak at 785 cm ⁇ 1 /Sum of the peak heights at 705 cm ⁇ 1 , 785 cm ⁇ 1 , and 815 cm ⁇ 1
• Percent para isomer content Height of peak at 815 cm ⁇ 1 /Sum of the peak heights at 705 cm ⁇ 1 , 785 cm ⁇ 1 , and 815 cm ⁇ 1
• the preferred toluene alkylate of this invention has an isomer distribution of about 25-35% ortho isomer, about 15-25% meta isomer and about 40-55% para isomer.
• the alkylated benzene and toluene used to prepare the sulfonates of this invention have a molecular weight of about 300 to about 315, preferably about 300 to about 308. They may comprise mixtures of monoalkylates and dialkylates.
• monoalkylate refers to the fact that the alkylate contains only one alkyl group derived from the propylene oligomers
• dialkylate refers to compounds which have two alkyl groups derived from the propylene oligomers. Neither of these terms is intended to refer to any other alkyl groups which may be on the aromatic ring, such as the methyl group in toluene.
• the alkylates used to prepare the sulfonates of this invention are preferably all monoalkylates. However, mixtures of monoalkylates and dialkylates may be used. When such mixtures are employed they generally contain about 75%, preferably about 85%, and more preferably about 90% to 100% monoalkylates, the balance, if any, being dialkylates.
• alkylates are prepared from oligomers of propylene, the alkyl group on the aromatic ring will all be branched chain alkyls.
• the alkylates of this invention do not contain linear alkyl groups.
• the alkylate is a mixture of ortho-, meta- and para-isomers of alkyltoluene.
• the mixture contains about 25-35% ortho-isomer, about 15-25% meta-isomer and about 40-55% para-isomer.
• the alkylates are sulfonated, and the sulfonic acid neutralized with an alkaline earth metal using methods known in the art.
• the sulfonates of this invention are overbased, i.e., they contain more alkaline earth metal than is needed to neutralize the sulfonic acid. They are considered low overbased materials since they have a relatively low Total Base Number (“TBN”).
• TBN Total Base Number
• Total Base Number refers to the amount of base equivalent to one milligram of KOH in one gram of additive. Thus, higher TBN numbers reflect more alkaline products and therefore a greater alkalinity reserve.
• the Total Base Number for an additive composition is readily determined by ASTM test method D664 or other equivalent methods.
• the low overbased alkylaryl sulfonates of this invention have Total Base Numbers from about 2 to about 30.
• the alkaline earth metal used to form the sulfonates may be calcium, barium or magnesium, with calcium being preferred.
• the overbasing reaction can be conducted using water as the solvent.
• a combination of water and an organic solvent such as 2-ethylhexanol, was employed.
• an organic solvent is more expensive than when water is the only solvent, and also leads to waste disposal problems.
• the reaction can be conducted using only water as the solvent, i.e., in the absence of an organic solvent.
• the overbasing reaction is conducted in the presence of lubricating oil. For purposes of this disclosure, such oils are not considered solvents for the overbasing reaction.
• the present invention provides a lubricating oil composition containing the low overbased alkaline earth alkylaryl sulfonates of this invention. It is possible for the lubricating oil composition to also contain sulfonates other than those of this invention, such as sulfonates in which the alkyl group in the alkylaryl moiety is linear. However, in the lubricating oil compositions and concentrates of this invention, more than 50% of the alkyl groups in the alkylaryl moiety are branched chain alkyls. Preferably, more than about 60-65% of the alkyls are branched, and still more preferably, essentially all (i.e. 95-100%) of the alkyls are branched.
• the lubricating oil also has an ashless dispersant and a zinc dialkyldithiophosphate.
• the lubricating oil also has a detergent selected from the group consisting of metal phenates, metal sulfonates, and metal salicylates.
• Other additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, pour point depressants, anti-oxidants, and a variety of other well-known additives More specifically, the following additive components exemplify the components that can be favorably employed in combination with the overbased, alkylbenzene or alkyltoluene sulfonates of the present invention
• Metallic detergents overbased sulfurized alkylphenates, overbased sulfonates, and overbased salicylates.
• Ashless dispersants alkenyl succinimides, alkenyl succinimides modified with other organic compounds, and alkenyl succinimides modified with boric acid, alkenyl succinic ester.
• Phenol type phenolic) oxidation inhibitors 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis(2,6-di-tert-butylphenol), 4,4′-bis(2-methyl-6-tert-butylphenol), 2,2′-(methylenebis(4-methyl-6-tert-butyl-phenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis(2,6-di-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-nonylphenol), 2,2′-isobutylidene-bis(4,6-dimethylphenol), 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethylmethyl
• Diphenylamine type oxidation inhibitor alkylated diphenylamine, phenyl-I-naphthylamine, and alkylated I-naphthylamine.
• metal dithiocarbamate e.g., zinc dithiocarbamate
• methylenebis dibutyldithiocarbamate
• Nonionic polyoxyethylene surface active agents polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate.
• Demulsifiers addition product of alkylphenol and ethyleneoxide, poloxyethylene alkyl ether, and polyoxyethylene sorbitane ester.
• EP agents Extreme pressure agents: zinc dialkyldithiophosphate (Zn-DTP, primary alkyl type & secondary alkyl type), sulfurized oils, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, benzyl iodide, fluoroalkylpolysiloxane, and lead naphthenate.
• Zn-DTP zinc dialkyldithiophosphate
• Sn-DTP primary alkyl type & secondary alkyl type
• sulfurized oils diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, benzyl iodide, fluoroalkylpolysiloxane, and lead naphthenate.
• Friction modifiers fatty alcohol, fatty acid, amine, borated ester, and other esters
• Multifunctional additives sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo phosphoro dithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compound, and sulfur-containing molybdenum complex compound
• Viscosity index improvers polymethacrylate type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
• the low overbased sulfonates of this invention are useful for imparting detergency and dispersancy properties to the lubricating oil. They provide lubricating compositions that have good coefficients of friction, are compatible with other additives, particularly sulfonates and phenates, do not cause the lubricating composition to skin, have good water tolerance, do not cause foaming, have good oxidative stability, and afford good rust protection.
• the amount of the alkylbenzene or alkyltoluene sulfonates of alkaline earth metals ranges from about 0.5% to 40% of the total lubricant composition, although preferably from about 1% to 25% of the total lubricant composition.
• Such lubricating oil compositions are useful in the crankcase of an internal combustion engine, such as gasoline engines and diesel engines, including passenger car, heavy duty on-road and off-road, railroad, natural gas and marine, such as trunk piston and slow speed crosshead. They are also useful in hydraulic applications.
• the lubricating oil composition can be used in a method of decreasing black sludge deposits, a method of decreasing piston deposits, or both.
• Such lubricating oil compositions employ a finished lubricating oil, which may be single or multigrade.
• Multigrade lubricating oils are prepared by adding viscosity index (VI) improvers.
• VI improvers are polyalkyl methacrylates, ethylene-propylene copolymers, styrene-diene copolymers, and the like.
• dispersant VI improvers which exhibit dispersant properties as well as VI modifying properties, can also be used in such formulations.
• the oil of lubricating viscosity used in such compositions may be mineral oil or synthetic oils of viscosity suitable for use in the crankcase of an internal combustion engine, such as gasoline engines and diesel engines, including passenger car, heavy duty on-road and off-road, railroad, natural gas and marine, such as trunk piston and slow speed crosshead.
• Crankcase lubricating oils ordinarily have a viscosity of about 1300 cSt 0° F. to 24 cSt at 210° F. (99° C.).
• the lubricating oils may be derived from synthetic or natural sources.
• Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
• Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
• Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6 to C 12 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such as didodecyl benzene, can be used.
• Useful synthetic esters include the esters of both monocarboxylic acids and polycarboxylic acids, as well as monohydroxy alkanols and polyols.
• Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate and the like.
• Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used.
• Blends of mineral oils with synthetic oils are also useful. For example, blends of 10% to 25% hydrogenated 1-trimer with 75% to 90% 150 SUS (100° F.) mineral oil gives an excellent lubricating oil base.
• a lubricating oil composition would contain
• Additive concentrates are also included within the scope of this invention.
• the concentrates of this invention comprise the alkylbenzene or alkyltoluene sulfonates of alkaline earth metals of the present invention, with at least one of the additives disclosed above.
• the concentrates typically contain sufficient organic diluent to make them easy to handle during shipping and storage.
• From 10% to 90% of the concentrate is organic diluent. From 0.5% to 90% of concentrate is the alkylbenzene or alkyltoluene sulfonates of alkaline earth metals of the present invention. The remainder of the concentrate consists of other additives.
• Suitable organic diluents which can be used include for example, solvent refined 100N, i.e., Cit-Con 100N, and hydrotreated 100N, i.e., RLOP 100N, and the like.
• the organic diluent preferably has a viscosity of from about 1 to about 20 cSt at 100° C.
• a lubricating oil composition is produced by blending a mixture of:
• the lubricating oil composition produced by that method might have a slightly different composition than the initial mixture, because the components may interact.
• the components can be blended in any order and can be blended as combinations of components.
• An alkylbenzene is prepared using a benzene:olefin molar ratio of 4:1.
• a stirred vessel 40.88 ml/minute of a propylene oligomer having an average molecular weight of 220, 56.93 ml/minute of benzene, and 102.19 mil/minute of hydrofluoric acid are added.
• the residence time in the vessel is 5.75 minutes at 38° C.
• the resulting product is placed in a settler where the HF (lower phase) is separated from the organic phase (alkylate and benzene).
• the organic phase is removed and the benzene is eliminated by stripping.
• Lower molecular weight alkylate i.e., alkylate having an alkyl group of 13 or fewer carbon atoms is removed by distillation.
• the alkylate product has a Bromine Number of 13 mg/100 grams.
• the final alkylate product has the following properties:
• Alkylbenzene (C 13 alkyl) 4% Alkylbenzene (alkyl higher than C 13 ) 96% Bromine Number 30 Molecular weight 302 Viscosity @40° C. 18.5 cSt Distillation (ASTM D86) 5% 321° C. 95% 376.8° C. Level of monoalkylbenzene (by IR) 87%
• the reaction is conducted in a sulfur trioxide falling film (height of the tube is 2 m.).
• Sulfur trioxide and the alkylbenzene product from Example 1 are introduced at the top of the tube.
• Alkylbenzene sulfonic acid is obtained at the bottom.
• the level of conversion is about 88%, and the mineral acidity (expressed as sulfuric acid) is about 0.6%.
• the acidity can be decreased by known methods.
• Hydrated lime (65.7 g), diluent oil (638.8 g) and a foam inhibitor (0.2 g) are placed in a suitable vessel, agitated and heated to 60° C.
• the alkylbenzene sulfonic acid prepared in Example 2 (549.1 g) is added to the vessel over a period of one hour. During this time, the temperature is increased from 60° C. to 85° C.
• 2-Ethylhexanol (100.7 g), calcium chloride (13.4 g), water (23 g) and a mixture of formic acid/acetic acid (9.1 g, 50/50 by weight) are added to the vessel. The temperature is raised to 100° C.
• the resulting filtered product has the following properties:
• Fraction 1 76 grams Fraction 2 268 grams Fraction 3 601 grams Fraction 4 (material left in 1070 grams distillation pot) Analysis of Fraction 4 shows the following properties: Viscosity (40° C.) 30.89 cSt Molecular weight (VPO) 323 Flash point (COC) 190° C. Bromine index 10.4 mg bromine/100 gm sample GLPC analysis of Fraction 4 shows it contains: Light Product 0.005% Heartcut Product 76.7% Heavies Product 23.3% Analysis by infrared shows the follow- ing percent isomer distribution: Ortho 17.0% Meta 13.8% Para 69.2%
• a toluene alkylate similar to that of Example 4 is sulfonated and the resulting alkyltoluene sulfonic acid (427 gms.), along with 573 gms.
• Exxon 100N oil are charged to a reaction vessel and stirred for 15 minutes.
• the resulting mixture is heated to 100° F. (37.8° C.) and 56.6 gms.
• Ca(OH) 2 is added. Heating to 190° F. (87.8° C.) is begun.
• the mixture is overheated to 216° F. (102.2° C.), so it is cooled to 192° F. (88.9° C.).
• One drop of foam inhibitor 56.5 gms. Water, and 15.1 gms.
• the reaction mixture is heated to 220° F. (104.4° C.) and held between 221° F. (105° C.) and 226° F. (107.8° C.) for 30 minutes.
• the reaction mixture is then heated to 265° F. (129.4° C.) over 20 minutes, and then to 320° F. (160° C.), with a 40 mm Hg vacuum being applied at 280° F. (137.8° C.).
• the resulting overbased alkyltoluene sulfonate has a Total Base Number of 23.5.

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• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1998
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